Zeolite ITQ-3

ABSTRACT

The present invention refers to a crystalline material of zeolitic nature named ITQ-3 characterized by its characteristic X-ray diffraction pattern and its microporous properties, to the process of preparation thereof characterized by the use of one or several organic additives in a reaction mixture that is made to crystallize by heating and to the use thereof in processes of separation and transformation of organic compounds, which material has the empirical formula x(M 1/n XO 2 ):yYO 2 :SiO 2  where x has a value lower than 0.15 and may be equal to zero; and y has a value lower than 0.1 and may be equal to zero; M is H +  or an inorganic cation of charge +n, X is a chemical element with oxidation state (Al, Ge, B and Cr), Y is a chemical element with oxidation state (Ti, Ge and V), and when x=0 and y=0 can be described as a new polymorphous of silica of microporous nature.

TECHNICAL FIELD

Microporous Crystalline Materials

BACKGROUND

Zeolites are microporous crystalline materials of variable compositioncharacterized by a TO₄ tetrahydra crystalline lattice (wherein Trepresents atoms in the formal oxidation state of +3 or +4, such as forexample Si, Ti, Al, Ge, B, Ga which all share their vertexes giving riseto a three-dimensional structure containing channels and/or cavities ofmolecular dimensions. When some of the atoms T have an oxidation statelower than +4, the crystalline lattice formed has negative charges whichare compensated by the presence of organic or inorganic cations in thechannels or cavities. Organic molecules and H₂O can also be located inthese channels and cavities, so in general, the chemical composition ofzeolites can be represented by the following empirical formula:

X(M_(1/n)XO₂):yYO₂:SiO₂

wherein M is one or several organic or inorganic cations with charge +n;X is one or several trivalent elements; Y is one or several tetravalentelements, generally Si; and R is one or several organic substances.Although the nature of M, X, Y and R and the values of x, y, z and wcan, in general, be varied by means of post-synthesis treatments, thechemical composition of a zeolite (just as it is synthesized or aftercalcination thereof) has a range characteristic of each zeolite and itspreparation method.

On the other hand, a zeolite is also characterized by its crystallinestructure, which defines a system of channels and cavities and givesrise to a specific X-ray diffraction pattern. In this way, zeolites aredifferentiated from each other by their range of chemical compositionplus their X-ray diffraction pattern. Both characteristics (crystallinestructure and chemical composition) also determine the physicochemicalproperties of each zeolite and the applicability thereof in differentindustrial processes.

DESCRIPTION OF THE INVENTION

The present invention refers to a microporous crystalline material ofzeolitic nature named ITQ-3, 5^(to) its method of obtainment and to itsapplications.

The material is characterized by its chemical composition and its X-raydiffraction pattern. In its anhydrous and calcined formed, the chemicalcomposition of ITQ-3 may be represented by the empirical formula:

X(M_(1/n)XO₂):yYO₂:SiO₂

wherein x has a value lower than 0.15; it may be equal to zero; and yhas a value lower than 0, 1; it may be equal to zero; M is H⁺ or aninorganic cation of charge +n; X is a chemical element with oxidationstate (Al, Ge, B, Cr) and Y is a chemical element with oxidation state+4 (Ti, Ge, V), when x=0 and y=0 the material can be described as a newpolymorphous of silica of microporous nature. In the preferredembodiment of the present invention, ITQ-3 has the composition, in acalcined and anhydrous state

x(HXO₂):SiO₂

wherein X is a trivalent element and x has a value lower than 0.1 andmay be equal to zero, in which case the material may be described bymeans of the formula SiO₂. However, it is possible, in terms of thesynthesis method and the calcination or subsequent treatments, theexistence of defects in the crystalline lattice, manifested by thepresence of Si—OH groups (silanols). These defects have not beenincluded in the above empirical formulae. In a preferred embodiment ofthe present invention, ITQ-3 has a very low concentration of this typeof defect (silanol concentration lower than 15% with respect to thetotal Si atoms, preferably lower than 6%, measured by nuclear magneticresonance spectroscopy of ²⁹Si in spinning angle).

The X-ray diffraction pattern of ITQ-3 just as it is synthesized asobtained by the powder method using a variable divergence slit and theCu Kα radiation, is characterized by the following values of 2^(θ)angles and relative intensities (I/I_(O)):

TABLE I 2θ I/I_(o) (°) (%)  8.54 100   9.28 85 10.07 15 11.04  5 12.41 5 13.60  7 14.17  3 15.70 14 17.02 11 17.58 15 18.10 85 18.84 20 19.2930 19.56 30 20.20 65 20.35 70 20.94 25 22.08  5 22.25  5 22.93  5 23.21 5 23.73 60 23.90 20 24.07 35 24.11 25 24.47 25 25.04 90 25.49 45 26.1210 26.63  8 27.14 10 27.83 10 28.23 10 28.85 10 29.08 10 30.33 20 31.5325 32.43 15 32.84 20 34.37  5

The positions and relative intensities of the peaks depend to a certaindegree on the chemical composition of the material (the patternrepresented in Table I refers to the material whose lattice isexclusively comprised of silicon oxide, SiO₂ and synthesized using aquaternary ammonium cation as a structure-directing agent). The relativeintensities may also be affected by phenomena of preferred orientationof the crystals, produced during preparation of the sample, while theprecision in the interplanar spacing measurement depends on the qualityof alignment of the goniometer. Moreover, calcination can yieldsignificant changes in the X-ray diffraction pattern, due to the removalof organic compounds retained during synthesis in the zeolite pores, sothat Table II represents the X-ray diffraction pattern of ITQ-3 ofcalcined ITQ-3 of composition SiO₂ is represented:

TABLE II I/I_(o) 2θ (%)  8.66 100   9.10 82 10.14 32 11.08  4 12.51  615.87  4 16.93  6 17.26  5 17.81  7 18.27 46 18.81  9 19.51 17 20.10 2120.38 11 20.74 10 22.17  9 22.26  8 23.90  9 24.04 12 24.17 15 24.27 1124.42 10 24.84 10 25.12 40 25.52  7 25.62  7 27.23  8 27.53  5 27.91  428.12  4 28.27  5 28.48  4 28.67  6 30.54 10 30.83  6 31.13  7 31.79 1332.48  6 32.84  4 33.06  8 33.46  3 33.48  3 34.15  4 34.26  4 34.64  334.77  3

The present invention also refers to the method of preparation of ITQ-3.This comprises thermal treatment at temperatures between 80 and 200° C.,preferably between 130 and 180° C., of a reaction mixture that containsa source of SiO₂ (such as, for example, tetraethylorthosilicate,colloidal silica, amorphous silica), an organic cation in hydroxideform, preferablyN,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1)octane (I)hydroxide, hydrofluoric acid and water. Alternatively, it is possible touse the organic cation as a salt (for example, a halide, preferablychloride) and to substitute hydrofluoric acid by a fluoride salt,preferably NH₄F. The reaction mixture is characterized by its relativelylow ph<12, preferably<11, and which may also be neutral or slightlyacidic.

Optionally, it is possible to add a source of another tetravalentelement Y and/or trivalent element X, preferably Ti or Al. The additionof this element may be done before heating the reaction mixture or in anintermediate time during said heating. Occasionally, it may beconvenient to add also in a certain time during the preparation of ITQ-3crystals (up to 15% by weight with respect to the total inorganicoxides, preferably up to 10% by weight) as cryst6allizer promoters(seeding). The composition of the reaction mixture in oxide formresponds to the general formula

RR₂O:aHF:xHXO₂:yYO₂:SiO₂:wH₂O

wherein X is one or several trivalent elements, preferably Al; Y is oneor several tetravalent elements; R is an organic cation, preferablyN,N-dimethyl-6-azonium-1,3,-trimethyl-6-bicyclo(3.2.1.)octane, and thevalues of r,a,x,y and w are in the ranges

R=0.05-1.0, preferably 0.1-0-75

A=0-1.5, preferably 0.1-1.5

X=0-0.15

Y=0-0.1

W=3-100, preferably 5-50, more preferably 7-50

The thermal treatment of the reaction mixture may be done in static orwith stirring of the mixture. Once the crystallization is finished thesolid product is separated and dried. Subsequent calcination attemperatures between 400 and 650° C., preferably between 450 and 600°C., produces the decomposition of the organic residue occluded in thezeolite and renders the free zeolitic channels.

This method of synthesis of ITQ-3 zeolite has the peculiarity that itdoes not require introduction of alkali cations in the reaction medium.As a consequence the organic cation R is the only cation that balancesthe lattice charges when the zeolite contains a trivalent element in itscrystalline lattice. Therefore, simple calcination to decompose theorganic cation leaves the zeolite in acid form, without the need toresort to cation exchange processes. Besides, the absence of alkalications in the reaction mixture allows synthesis of the materialcontaining elements such as Ti(IV), which would not be possible tointroduced in the lattice in the presence of these cations (see, forexample, M. A. Camblor, A. Corma, J. Pérez-Pariente, Zeolites, vol. 13,82-87, 1993). Thus, once calcined the material has the general formula

X(HXO₂):yYO₂:SiO₂

wherein x is lower than 0.15, and may be equal to 0; y is lower than0.1, and may also be zero; X is a chemical element with oxidation stateof +3 and Y is a chemical element with an oxidation state of +4.

The crystalline material of the present invention may be used in severalapplications, such as, for example, in processes for the separation oflinear and branched paraffin compounds. Hence, a mixture of isobutaneand n-butane or isopentane and n-pentane may be enriched in the morebranched isomer by selective adsorption of the linear paraffin by themicroporous material of the present invention. Said material isparticularly suitable for use in this type of process due to its highadsorption capacity (micropore volume determined by adsorption ofN₂=0.23 cm³/g) and its small pore size (maximum opening ≦5.5 Å,determined by adsorption of Ar, using the Horvath-Kawazoe formalism).

Likewise and preferably using the pure silica polymorph, it is possibleto separate by selective adsorption the n-olefins of mixtures containingnormal and isoolefins, enriching the final stream in isoolefins. Ingeneral, this material would allow the separation of organic compounds,which may or may not contain heteroatoms, with sizes smaller than 5-5.5Å present in mixtures also containing organic compounds of larger sizes.Due to the hydrophobic characteristics of the silica polymorph, ITQ-3would permit selective adsorption of organic compounds with kineticdiameter smaller than 5-5.5 Å present in polar media, such as, forexample, in aqueous media.

From the view point of its use as a catalyst, this material, whenprepared in the acid form and which may or may not contain supportedtransition metals such as Pt, Pd or Ni, allows the selective crackingand hydrocracking of linear alkanes with respect to the branched ones orto larger hydrocarbons, thus being adequate as a catalyst or catalyticcracking additive and as a catalyst in the “selectoforming” type processthat involves hydrocracking of the stream coming from the reformed unitfor the purpose of removing n-paraffins.

Likewise, ITQ-3 gives good results as an alkane and alkene catalyst forthe purpose of producing high yields of ethylene, propylene and butene,thus being suitable as a catalyst for production processes of shortolefins by catalytic steam cracking. Moreover, its possibilities ofselectively cracking linear paraffins makes it a good catalyst fordewaxing processes. Finally, this material is a good catalyst inprocesses of transformation of methanol into olefins.

EXAMPLES Example 1

This example illustrates the preparation ofN,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1.)octane hydroxide.

38.32 of 1,3,3-trimethyl-6-azabicyclo (3.2.1.)octane (Aldrich), 220 g ofChCl₃ (SDS synthesis grade) and 82.50 g of potassium carbonatesesquihydrate (99%, Aldrich) are introduced in a 500 ml flask. To thismixture 31 ml of CH₃I (99% Aldrich) are added dropwise and understirring in an ice bath. After seven days of stirring at roomtemperature the mixture is filtered and the liquid is evaporated in arotovap. After washing the obtained solid with ethyl acetate and dryingit, 71.37 g of a solid is obtained, whose nuclear magnetic resonancespectrum in CDCl₃ indicates that it is a nucleophilic substitutionproduct, namely, the iodide of the organic cation corresponding to thedimethylation of the amine. Chemical analysis of the product 45.5% C,4.42% N, 7.54% H, Theoretical: 46.51% C, 4.53% N, 7.82% H) confirms thisresult.

The hydroxide form of the structure-directing agent is obtained by anionexchange using Dowex 1 (Sigma) resin, previously washed with distilledwater until pH=7. To a solution of 9.27 g of the former product in194.02 g of water, 221.73 g of resin were added and left under stirringfor about 12 hours. After filtering the resin, the solution was titratedwith HCl (aq) using phenolphthalein as indicator, and finding anefficiency of 96.62% in the exchange. This solution could beconcentrated in the rotovap for use in the synthesis of ITQ-3, and itsfinal concentration is obtained by means of further titration.

Example 2

This example illustrates the preparation of pure silica ITQ-3, usingN,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1.)octane hydroxide asthe organic structure-directing agent.

12.08 g. Of tetraethylorthosilicate (TEOS) were added to 23.02 g. Of asolution containing 1.26 moles ofN,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1.)octane hydroxideper 1000 g, obtained in the way described in Example 1, and the mixturewas stirred, allowing evaporation of the ethanol produced in thehydrolysis of TEOS, along with some water. After 6 hours of stirring(weight loss: 18.99 g) 0.57 g of water and 1.21 g. Of HF (aq) (48%Aldrich) were added. The paste obtained is introduced in apolytetrafluoroethylene lined autoclave and kept at 150° C. underrotation (60 rpm) for 19 days. Then, the autoclave was cooled down, thecontents were filtered and the solid washed with water and dried at 100°C. Its X-ray diffraction pattern is shown in Table 1. After calcinationat 580° C. the white solid obtained has the diffractogram of Table 2.Chemical analysis by atomic absorption spectroscopy of the calcinedmaterial reveals that, within the detection limits of the technique andthe experimental error, the obtained product is silica (SiO₂). ²⁹Si MASNMR spectroscopy measurements indicate that the calcined materialcontains a very low proportion of connectivity defects, as inferred fromthe ratio of SiOH to total Si (calculated as the quotient between thearea of the peak centered at 101 ppm and the total area of all of thepeaks). N₂ adsorption measures indicate a surface area of 455 m²/g(B.E.T. method) and a micropore volume of 0.23 cc/g. The solid state¹³NMR spectrum of the material just as it was made clearly shows thepresence of the organic cation occluded in the inorganic crystallinelattice, as well as the elemental analysis which gives molar ratios arepractically those of the organic cation (C/N=11.8, H/N=23.4).

Examples 3-6

These examples illustrate the preparation of pure silica ofAl-containing ITQ-3, whether in the presence or absence of seeds.

The same experimental procedure of example 2 was followed. The synthesisconditions are listed in Table 3. In examples 4 and 5 metal aluminum andaluminum nitrate nonahydrate were used, respectively, as an aluminumsource. The OH_(ef) formalism is defined as the difference between theadded OH moles and those employed by the aluminum to reach tetrahydralcoordination. All the crystallizations were carried out under stirring(60 r.p.m.). In all cases high crystallinity ITQ-3 was obtained.

TABLE III Molar ratios SiO₂/ seeds Si/Al example Al₂O₃ T/SiO₂ OH_(ef)/FH₂O/SiO₂ % (SiO₂) T(° C.) t (days) (solid) 3 0.48 1 14.6 2.7 135 14 4 600.52 1 15 — 150 35 38.8 5 104 0.55 1 17.4 4.7 135 14 55.8 6 53 0.69 116.5 4.7 135 13 32.7

What is claimed is:
 1. A microporous crystalline material of zeoliticnature with an X-ray diffraction pattern substantially in accordancewith Tables I and II for the material as synthesized and aftercalcination, respectively, and with a chemical composition in thecalcined and anhydrous state represented by an empirical formula x(M_(1/n)XO₂):yYO₂:SiO₂ wherein x has a value lower than 0.15; y has avalue lower than 0.1; M is H⁺ or an inorganic cation of charge +n; X,when present, is a chemical element with oxidation state +3 being atleast one of Al, Ge, B and Cr; and Y, when present, is a chemicalelement with oxidation state +4 being at least one of Ti, Ge and V.
 2. Acrystalline material according to claim 1 having a chemical compositionin the calcined and anhydrous state represented by the empirical formulax(HXO₂):yYO₂:SiO₂ wherein X, when present, is a trivalent element beingat least one of Al, B, Ga, and Cr; Y, when present, is a tetravalentelement different from Si and being at least one of Ti, Ge and V; x hasa value lower than 0.15, y has a value lower than 0.1, and wherein thecation H⁺ may be exchanged by other mono-, di- or trivalent organic orinorganic cations.
 3. A crystalline material in accordance with claim 1having a chemical composition in the calcined and anhydrous staterepresented by the empirical formula x(HAlO₂):SiO₂ wherein x has a valuelower than 0.15 and may also be equal to zero and wherein the H⁺ cationmay be exchanged by other mono-, di- or trivalent organic or inorganiccations.
 4. A crystalline material in accordance with claim 1 having achemical composition in the calcined and anhydrous state represented bythe formula SiO₂.
 5. A method of using the microporous crystallinematerial of claim 1 in a process of separation of iso- and normalparaffins, the method comprising adding a suitable amount of thematerial and selectively adsorbing the normal paraffins to the material.6. A method of using the microporous crystalline material of claim 1 ina process of separation of isobutane and n-butane, the method comprisingadding a suitable amount of the material and selectively adsorbingn-butane to the material.
 7. A method of using the microporouscrystalline material of claim 1 in a process of separation of isopentaneand n-pentane, the method comprising adding a suitable amount of thematerial and selectively adsorbing n-pentane to the material.
 8. Amethod of using the microporous crystalline material of claim 1 inprocesses of separation of iso and normal olefins, the method comprisingadding a suitable amount of the material and selectively adsorbingn-olefins to the material.
 9. A method of using the microporouscrystalline material of claim 1 in a process of separation of isobuteneand normal butene, the method comprising adding a suitable amount of thematerial and selectively adsorbing n-butene to the material.
 10. Amethod of using the microporous crystalline material of claim 1 in aprocess of separation of isopentene and normal pentene, the methodcomprising adding a suitable amount of the material and selectivelyadsorbing n-pentene to the material.
 11. A method of using themicroporous material of claim 1, in a process of separation of organiccompounds, selected from organic compounds comprising heteroatoms,organic compounds not comprising heteroatoms and mixtures thereof, theorganic compounds having a kinetic diameter smaller than 5-5.5 Å, themethod comprising adding a suitable amount of the material andselectively adsorbing to the material the organic compounds havingkinetic diameters smaller than 5-5.5 Å from mixtures containingcompounds with a kinetic diameter larger than 5-5.5 Å.
 12. A method ofusing the microporous crystalline material of claim 1 in a process ofseparation of organic compounds with a kinetic diameter smaller than 5.5Å from polar streams, for the purpose of purifying said streams, themethod comprising adding a suitable amount of the material to saidstream and selectively adsorbing the organic compounds to the material.13. A method according to claim 12, wherein the polar stream is anaqueous polar stream.
 14. A method of using the microporous crystallinematerial of claim 1 as a catalyst in a process of selective cracking andhydrocracking of linear paraffins, linear olefins and mixtures thereof,the method comprising contacting the linear paraffins with a suitableamount of the material.
 15. A method of using the microporouscrystalline material of claim 1 as a “post-reformate” catalyst in aprocess for post-reformation of gasoline, the method comprisingcontacting the gasoline being subject to reformation, with a suitableamount of the material.
 16. A method of using the microporouscrystalline material of claim 1, in a catalytic steam cracking processto produce a stream with a high content of ethylene, propylene andbutene by cracking an initial stream of alkanes and alkenes, the methodcomprising contacting said initial stream with a suitable amount,whereby the material is used as a catalyst.
 17. A method of using themicroporous crystalline material of claim 1 as a catalyst in a dewaxingprocess by selective cracking of n-paraffins, the method comprisingcontacting the n-paraffins with a suitable amount of the material.
 18. Amethod of using the microporous crystalline material of claim 1 as acatalyst in processes of conversion of methanol into olefins, the methodcomprising contacting the methanol with a suitable amount of thematerial.
 19. A method of using the microporous crystalline material ofclaim 1, in a catalytic cracking process to produce a stream with a highcontent of ethylene, propylene and butene by cracking an initial streamof alkanes and alkenes, the method comprising contacting said initialstream with a suitable amount, whereby the material is used as acatalyst.
 20. A process for synthesizing a crystalline material ofzeolitic nature with an X-ray diffraction pattern substantially inaccordance with Tables I and II for the material as synthesized andafter calcination, respectively, and with a chemical composition in thecalcined and anhydrous state represented by an empirical formulax(M_(1/n)XO₂):yYO₂:SiO₂ wherein x has a value lower than 0.15; y has avalue lower than 0.1; M is H⁺ or an inorganic cation of charge +n; X,when present, is a chemical element with oxidation state +3 being atleast one of Al, Ge, B and Cr and Y, when present, is a chemical elementwith oxidation state +4 being at least one of Ti, Ge and V, wherein areaction mixture that contains a source of SiO₂, an organic cation R⁺being N,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1.)octane, asource of F, a source, when present, of one or several tetravalentelements Y different from Si, a source, when present, of one or severaltetravalent elements X, and water, is subjected to heating at atemperature between 80 and 200° C. until achieving crystallizationthereof and wherein the reaction mixture has a composition, in terms ofmolar ratios of oxides, of X₂O₃/SiO₂=0-0.1, ROH/SiO₂=0.05-2.0,F/Si=0.2-1.5, YO₂/SiO₂=0-0.1 H₂O/SiO₂=3-100.
 21. A process according toclaim 20, wherein the reaction mixture does not comprise a source of atetravalent element other than Si, and has a composition in terms ofmolar ratios of oxides, of X₂O₃/SiO₂=0-0.1, ROH/SiO₂=0.05-2.0,F⁻/Si=0-2, and H₂O/SiO₂=3-100.
 22. A process according to claim 21,wherein the reaction mixture has a composition in terms of molar ratiosof oxides, of X₂O₃/SiO₂=0-0.05 ROH/SiO₂=0.2-1.5 F⁻/Si=0.2-1.5H₂O/SiO₂=5-50.
 23. A process according to claim 21, wherein the reactionmixture has a composition in terms of molar ratios of oxides, ofX₂O₃/SiO₂=0-0.05 ROH/SiO₂=0.2-1.5 F⁻/Si=0.2-1.5 H₂O/SiO₂=7-50.
 24. Aprocess according to claim 21, wherein the reaction mixture does notcomprise a source of a tetravalent element other than Si, X₂O₃ is Al₂O₃,and the reaction mixture has a composition, in terms of molar ratios ofoxides, of Al₂O₃/SiO₂=0-0.1, ROH/SiO₂=0.05-2.0, F⁻/Si=0-2, andH₂O/SiO₂=3-100.
 25. A process according to claim 24, wherein thereaction mixture has a composition, in terms of molar ratio of oxides,of Al₂O₃/SiO₂=0-0.05 ROH/SiO₂=0.2-1.5 F⁻/Si=0.2-1.5 H₂O/SiO₂=7-50.
 26. Aprocess according to claim 20, wherein the reaction mixture does notcomprise a source of a tetravalent element other than Si, does notcomprise a source of a trivalent element, and has a composition, interms of molar ratios of oxides, of ROH/SiO₂=0.05-2-0, F⁻/Si=0-2, andH₂O/SiO₂=3-100.
 27. A process according to claim 26, wherein thereaction mixture has a composition, in terms of molar ratios of oxides,of Al₂O₃/SiO₂=0-0.05 ROH/SiO₂=0.2-1.5 F⁻/Si=0.2-1.5 H₂O/SiO₂=5-50.
 28. Aprocess according claim 26, wherein the reaction mixture has acomposition, in terms of molar ratios of oxides, of ROH/SiO₂=0.2-1.5F/Si=0.2-1.50 H₂O/SiO₂=5-50.
 29. A process according to claim 26,wherein the reaction mixture has a composition, in terms of molar ratiosof oxides, of ROH/SiO₂=0.2-1.5 F⁻/Si=0.2-1.50 H₂O/SiO₂=7-50.
 30. Aprocess according to claim 20, wherein the reaction mixture does notcomprise a source of a trivalent element and has a composition, in termsof molar ratios of oxides, of ROH/SiO₂=0.05-2.0, F⁻/Si=0-2,YO₂/SiO₂=0-4.1, and H₂O/SiO₂=3-100.
 31. A process according to claim 30,wherein the reaction mixture has a composition, in terms of molar ratiosof oxides, of ROH/SiO₂=0.2-1.5 F⁻/Si=0.2-1.50 YO₂/SiO₂=0-0.1H₂O/SiO₂=5-50.
 32. A process according to claim 30, wherein the reactionmixture has a composition, in terms of molar ratios of oxides, ofROH/SiO₂=0.2-1.5 F⁻/Si=0.2-1.5 YO₂/SiO₂=0-0.1 H₂F/SiO₂=7-50.
 33. Aprocess according to claim 20, wherein the organic cation is selectedfrom N,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1.)octanehydroxide, N,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1.)octanesalt, and mixtures thereof, and the fluoride anion is added in the formof ammonium fluoride, such that reaction mixture achieves a pH fromslightly acidic to
 12. 34. A process according to claim 33, wherein thepH of the reaction mixture is from slightly acidic to
 11. 35. A processaccording to claim 20, wherein to the reaction mixture is added anamount of crystalline material as crystallization promoter, said amountbeing 0.05 to 15% by weight with regard to the total silica added.
 36. Aprocess according to claim 35, herein the amount of crystalline materialadded as crystallization promoter is comprised in the range of 0.05 to5% by weight with regard to the total silica added.
 37. A processaccording to claim 20, wherein the reaction mixture is essentially freeof alkali cations, the only limitation being a possible content ofalkali impurities of reactants used.
 38. A process according to claim20, wherein a source of a tetravalent element different than Si is addedor a trivalent element is added in an intermediate step during heatingof the reaction mixture.
 39. A process according to claim 20, whereinthe reaction mixture is subjected to heating at a temperature between130 and 180° C.
 40. A process according to claim 20, wherein thereaction mixture has a composition, in terms of molar ratios of oxides,of X₂O₃/SiO₂=0-0.5 ROH/SiO₂=0.2-1.50 F⁻/Si=0.2-1.50 YO₂/SiO₂=0-0.1.H₂O/SiO₂=5-50.
 41. A process according to claim 20, wherein the reactionmixture has a composition, in terms of molar ratios of oxides, ofX₂O₃/SiO₂=0-0.5 ROH/SiO₂=0.2-1.50 F⁻/Si=0.2-1.50 YO₂/SiO₂=0-0.1H₂O/SiO₂=7-50.
 42. A process according to claim 20, wherein the sourceof the tetravalent element different from Si is added in an intermediatestep during heating of the reaction mixture.
 43. A process according toclaim 20, wherein the source of the trivalent element is added in anintermediate step during heating of the reaction mixture.
 44. Amicroporous crystalline material of zeolitic nature with an X-raydiffraction pattern substantially in accordance with Tables I and II forthe material as synthesized and after calcination, respectively, andwith a chemical composition in the calcined and anhydrous staterepresented by an empirical formula x(M_(1/n)XO₂):yYO₂:SiO₂ wherein xhas a value lower than 0.15; y has a value lower than 0.1; M is H⁺ or aninorganic cation of charge +n; X, when present, is a chemical elementwith oxidation state +3 being at least one of Al, Ge, B and Cr and Y,when present, is a chemical element with oxidation state +4 being atleast one of Ti, Ge and V, and wherein the crystalline material has beenobtained from a reaction mixture comprising a source of F−.
 45. Acrystalline material according to claim 44 having a chemical compositionin the calcined and anhydrous state represented by the empirical formulax(HXO₂):yYO₂:SiO₂ wherein X, when present, is a trivalent element beingat least one of Al, B, Ga and Cr; Y, when present, is a tetravalentelement different from Si being at least one of Ti, Ge and V, x has avalue lower than 0.15, y has a value lower than 0.1, and wherein thecation H⁺ may be exchanged by other mono-, di- or trivalent organic orinorganic cations.
 46. A crystalline material in accordance with claim44 having a chemical composition in the calcined and anhydrous staterepresented by the empirical formula x(HAlO₂):SiO₂ wherein x has a valuelower than 0.15 and may also be equal to zero and wherein the H⁺ cationmay be exchanged by other mono-, di- or trivalent organic or inorganiccations.
 47. A crystalline material in accordance with claim 44 having achemical composition in the calcined and anhydrous state represented bythe formula SiO₂.
 48. A method of using the microporous crystallinematerial of claim 44, in a process of separation of iso- and normalparaffins, the method comprising adding a suitable amount of thematerial and selectively adsorbing the normal paraffins to the material.49. A method of using the microporous crystalline material of claim 44,in a process of separation of isobutane and n-butane, the methodcomprising adding a suitable amount of the material and selectivelyadsorbing n-butane to the material.
 50. A method of using themicroporous crystalline material of claim 44, in a process of separationof isopentane and n-pentane, the method comprising adding a suitableamount of the material and selectively adsorbing n-pentane to thematerial.
 51. A method of using the microporous crystalline material ofclaim 44, in processes of separation of iso- and normal olefins, themethod comprising adding a suitable amount of the material andselectively adsorbing n-olefins to the material.
 52. A method of usingthe microporous crystalline material of claim 44, in a process ofseparation of isobutene and normal butene, the method comprising addinga suitable amount of the material and selectively adsorbing n-butene tothe material.
 53. A method of using the microporous crystalline materialof claim 44, in a process of separation of isopentene and normalpentene, the method comprising adding a suitable amount of the materialand selectively adsorbing n-pentene to the material.
 54. A method ofusing the microporous material of claim 44, in a process of separationof organic compounds, selected from organic compounds comprisingheteroatoms, organic compounds not comprising heteroatoms and mixturesthereof, the organic compounds having a kinetic diameter smaller than5-5.5 Å, the method comprising adding a suitable amount of the materialand selectively adsorbing to the material the organic compounds havingkinetic diameters smaller than 5-5.5 Å from mixtures containingcompounds with a kinetic diameter larger than 5-5.5 Å.
 55. A method ofusing the microporous crystalline material of claim 44, in a process ofseparation of organic compounds with a kinetic diameter smaller than 5.5Å from polar streams, for the purpose of purifying said streams, themethod comprising adding a suitable amount of the material to saidstream and selectively absorbing the organic compounds to the material.56. A method of using the microporous crystalline material of claim 44,as a catalyst in a process of selective cracking and hydrocracking oflinear paraffins, linear olefins and mixtures thereof, the methodcomprising contacting the linear paraffins with a suitable amount of thematerial.
 57. A method of using the microporous crystalline material ofclaim 44, as a “postreformate” catalyst in a process for postreformationof gasoline, the method comprising contacting the gasoline being subjectto reformation, with a suitable amount of the material.
 58. A method ofusing the microporous crystalline material of claim 44, in a catalyticsteam cracking process to produce a stream with a high content ofethylene, propylene and butene by cracking an initial stream of alkanesand alkenes, the method comprising contacting said initial stream with asuitable amount of the material, whereby the material is used as acatalyst.
 59. A method of using the microporous crystalline material ofclaim 44, as a catalyst in a dewaxing process by selective cracking ofn-paraffins, the method comprising contacting the n-paraffins with asuitable amount of the material.
 60. A method of using the microporouscrystalline material of claim 44, as a catalyst in processes ofconversion of methanol into olefins, the method comprising contactingthe methanol with a suitable amount of the material.
 61. A method ofusing the microporous crystalline material of claim 44, in a catalyticcracking process to produce a stream with a high content of ethylene,propylene and butene by cracking an initial stream of alkanes andalkenes, the method comprising contacting said initial stream with asuitable amount, whereby the material is used as a catalyst.
 62. Amicroporous crystalline material of zeolitic nature with an X-raydiffraction pattern of Tables I and II for the material as synthesizedand after calcination, respectively, and with a chemical composition inthe calcined and anhydrous state represented by an empirical formulax(M_(1/n)/XO₂):yYO₂:SiO₂ wherein x has a value lower than 0.15; y has avalue lower than 0.1; M is H⁺ or an inorganic cation of charge +n; X,when present, is a chemical element with oxidation state +3 being atleast one of Al, Ge, B and Cr and Y, when present, is a chemical elementwith oxidation state +4 being at least one of Ti, Ge and V.